Glasses with improved tempering capabilities

ABSTRACT

The disclosure relates to glass compositions having improved thermal tempering capabilities. The disclosed glass compositions have high coefficients of thermal expansion and Young&#39;s moduli, and are capable of achieving high surface compressions. A method of making such glasses is also provided.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/640,993 filed on Feb. 21, 2020, which claims the benefit of priorityunder 35 U.S.C. § 371 of International Application No.PCT/US2018/047859, filed on Aug. 24, 2018, which claims the benefit ofpriority under 35 U.S.C. § 119 of U.S. Provisional Application Ser. No.62/549,507 filed on Aug. 24, 2017, the content of each of which isrelied upon and incorporated herein by reference in their entirety.

FIELD OF DISCLOSURE

The disclosure relates to highly temperable glass compositions. Moreparticularly, the disclosure relates to glasses having improvedtempering when compared to common soda lime glasses. Even moreparticularly, the disclosure relates to glass compositions with highcoefficients of thermal expansion and high Young's moduli for use with athermal tempering process.

BACKGROUND

In thermal tempering, a glass product is heated to near the softeningtemperature and then rapidly quenched. As a result, the glass willpossess a lower surface temperature than the interior during cooling.The temperature difference is maintained until the surface of the glasscools to room temperature. As the center of the glass cools more slowlyto room temperature it contracts to a smaller specific volume while thehigh specific volume of the surface layer remains unchanged. This leadsto a surface compressive layer that gives tempered glass its strength.The difference in specific volume is in majority due to differences inthe thermal expansion of the glass upon cooling, while to a lesserextent from a fictive temperature difference between the surface and thebulk. To a first approximation, the stress distribution in thermallytempered glass can be represented by a simple parabola, with themagnitude of the surface compressive stress approximately equal to twicethe center tension.

Thermally tempered glass, sometimes called safety glass, is oftenapplied in situations where safe fracture behavior is required toprevent injury in the case of failure, being used to strengthenautomobile side and rear windows, as well as object such as showerdoors. It is desired that when thermally tempered glass breaks, unlikeannealed glass, it shatters into rock-salt like pieces which do not havesharp edges or needle-like shapes. It is for this reason thatcharacterizing the fracture behavior of thermally tempered glass is ofparamount importance. The desired fracture behavior is called “dicing”and occurs when the glass has achieved full temper.

In addition to the safety aspect of thermally tempered glass, temperingstrengthens the glass, making it more damage resistant and durable.Because of the increased durability, tempered glass can be used inapplications where normal glass would quickly break—for example,automotive windshields, where the glass may impacted by rocks or otherhard materials. Due to the increase in glass use in architectural,automotive, and electronic device applications, there is a continuedneed for strengthened glasses having improved tempering capabilities.

FIG. 1 is a graph of transmittance as a function of wavelength forcompositions disclosed herein.

DETAILED DESCRIPTION

In the following description, whenever a group is described ascomprising at least one of a group of elements and combinations thereof,it is understood that the group may comprise, consist essentially of, orconsist of any number of those elements recited, either individually orin combination with each other. Similarly, whenever a group is describedas consisting of at least one of a group of elements or combinationsthereof, it is understood that the group may consist of any number ofthose elements recited, either individually or in combination with eachother. Unless otherwise specified, a range of values, when recited,includes both the upper and lower limits of the range as well as anyranges therebetween. As used herein, the indefinite articles “a,” “an,”and the corresponding definite article “the” mean “at least one” or “oneor more,” unless otherwise specified. It also is understood that thevarious features disclosed in the specification and the drawings can beused in any and all combinations.

Where a range of numerical values is recited herein, comprising upperand lower values, unless otherwise stated in specific circumstances, therange is intended to include the endpoints thereof, and all integers andfractions within the range. It is not intended that the scope of theclaims be limited to the specific values recited when defining a range.Further, when an amount, concentration, or other value or parameter isgiven as a range, one or more preferred ranges or a list of upperpreferable values and lower preferable values, this is to be understoodas specifically disclosing all ranges formed from any pair of any upperrange limit or preferred value and any lower range limit or preferredvalue, regardless of whether such pairs are separately disclosed.Finally, when the term “about” is used in describing a value or anend-point of a range, the disclosure should be understood to include thespecific value or end-point referred to. When a numerical value orend-point of a range does not recite “about,” the numerical value orend-point of a range is intended to include two embodiments: onemodified by “about,” and one not modified by “about.”

As used herein, the term “about” means that amounts, sizes,formulations, parameters, and other quantities and characteristics arenot and need not be exact, but may be approximate and/or larger orsmaller, as desired, reflecting tolerances, conversion factors, roundingoff, measurement error and the like, and other factors known to those ofskill in the art. It is noted that the terms “substantially” may beutilized herein to represent the inherent degree of uncertainty that maybe attributed to any quantitative comparison, value, measurement, orother representation. These terms are also utilized herein to representthe degree by which a quantitative representation may vary from a statedreference without resulting in a change in the basic function of thesubject matter at issue. Thus, a glass that is “free of Al₂O₃” is one inwhich Al₂O₃ is not actively added or batched into the glass, but may bepresent in very small amounts as a contaminant (e.g., 500, 400, 300,200, or 100 parts per million (ppm) or less or).

Unless otherwise specified, all compositions are expressed in terms ofmole percent (mol %). Coefficients of thermal expansion (CTE) areexpressed in terms of 10⁻⁷/° C. and represent a value measured over atemperature range from 25° C. to 300° C., unless otherwise specified.The low temperature CTE (LTCTE) is measured at 25° C. and expressed interms of 10⁻⁷/° C. The high temperature CTE (HTCTE) is measured at 300°C. and expressed in terms of 10⁻⁷/° C. The sum of the LTCTE and theHTCTE is expressed in terms of 10⁻⁷/° C. The density in terms ofgrams/cm³ was measured via the Archimedes method (ASTM C693). Young'smodulus, shear modulus, and Poisson's Ratio were measured via the ASTMC623 standard.

Glass Compositions

In thermal tempering, a glass product is heated to near the softeningtemperature and then rapidly quenched. As a result, the glass willpossess a lower surface temperature than the interior during cooling.The temperature difference is maintained until the surface of the glasscools to room temperature. As the center of the glass cools more slowlyto room temperature it contracts to a smaller specific volume while thehigh specific volume of the surface layer remains unchanged. This leadsto a surface compressive layer that gives tempered glass its strength.The difference in specific volume is due to a combination of differencesin the thermal expansion of the glass upon cooling and from a fictivetemperature difference between the surface and the bulk. To a firstapproximation, the stress distribution in thermally tempered glass canbe represented by a simple parabola, with the magnitude of the surfacecompressive stress approximately equal to twice the center tension.

When thermally tempered glass breaks, unlike annealed glass, it shattersinto rock-salt like pieces which do not have sharp edges or needle-likeshapes. This behavior is particularly useful for situations where safefracture behavior is necessary and it is for this reason thatcharacterizing the fracture behavior of thermally tempered glass is ofparamount importance. The desired fracture behavior is called “dicing”and occurs when the glass has achieved full temper. The dicing thresholdof tempered glass is an arbitrarily defined fracture behavior which canbe considered “safe” to the user in the event of glass failure.Standards exist worldwide such as ASTM C1048 and ANSI Z97.1 in theUnited States, EN12150-1 in Europe, GOST 5727-88 in Russia, JIS R 3206in Japan, and GB 15763.2 in China (all of which are hereby incorporatedby reference). The standards are nearly identical across countries inthat a fragmented piece of tempered soda-lime glass is required tocontain at least 30-40 fragments in an area of 50 mm×50 mm (1.6fragments/cm²) for thick glasses >3 mm, while Japanese standards inparticular require at least 60 fragments in the case of thinner glass.

It is of interest to predict the ability of a glass composition toproduce stresses during thermal tempering. The simplest approximationone can make in forming a more general expression is to assume that forany chosen combination of glass thickness and quenching rate, the stressformed due to thermal strain is a fraction of the maximum possible.Therefore a general expression for the compressive tempering stressformed when quenched from a constant viscosity can be expressed as:

o _(Cs) =C(h,t,η)*Ψ(E,α _(CTE) ^(s),α_(CTE) ^(L) ,T _(soft) ,T_(strain))

where □^(s) is the CTE of the glass in solid form, □^(L) is the CTE ofthe glass in liquid form, T_(soft) is the softening point temperature,T_(strain) is the strain point temperature, and the constant, Ψ, is amaterial property called the “temperability parameter” and isrepresentative of the maximum thermal strain that can be formed if thesurface was frozen upon quenching. The maximum thermal strain can beroughly estimated by a 2-step integration of the thermal expansion as afunction of temperature and general glass properties. The thermalexpansion coefficient (CTE) is assumed to be a constant from roomtemperature to the strain point, and then constant again from the strainpoint to softening. With this in mind and with the assumption that roomtemperature is close to 0° C., a more general “temperability parameter”can be expressed as:

Ψ=E*[T _(stain)*α_(CTE) ^(s)+α_(CTE) ^(L)*(T _(soft) −T _(strain))]

where E is in GPa, temperatures are given in ° C., and α is in ° C.⁻¹.It can be seen that this expression contains a more general form of thevolumetric strain calculated using the strain point of the glass betweenglassy and liquid behavior.

By measuring a few standard properties for a given glass, it is possibleto estimate the temper stresses that would be expect to form if theconstant, C(h,t,η), is known. This constant has been evaluated usingmodeling for a wide range of known compositions, and from thecalculation of Ψ, the relative temperability of various glasscompositions can be quickly compared to one another. When thetemperabilities of a variety glass compositions are calculated, theresults show that various combinations of properties can reach a similarendpoint and that glasses vast differences in the compositions andproperties can be nearly indistinguishable in terms of temperability.

The glasses disclosed herein have high coefficients of thermal expansionand high Young's moduli and can be used with a thermal tempering processto obtain improved tempering when compared to commercially availableglasses. The glasses described herein are needed to satisfy a growingdemand for stronger but thinner thermally strengthened glasses forcommercial electronics, automotive and architectural applications wheredurability and/or scratch resistance are desired along with a “safe”break pattern. As glass becomes thinner, it becomes harder to produceany thermal tempering stresses at all and the central tension requiredfor a safe ‘dicing” fracture pattern increases—producing a compoundchallenge. Developing glasses which produce enhanced temper stresses canhelp to meet this challenge. Additionally, the glasses must also retaina significant chemical durability, as they will likely be exposed to theelements for extended periods of time.

It has been found that glasses having temperability parameters, Ψ, of0.8 or higher, 0.85 or higher, or even 0.9 or higher, are capable ofincreased thermal tempering. In some embodiments, to improvetemperability, it has been found that the low temperature coefficient ofthermal expansion (LTCTE) should be 5.5×10⁻⁷/° C. or greater. In someembodiments, it has been found that the high temperature coefficient ofthermal expansion (HTCTE) should be 27×10⁻⁷/° C. or greater. In someembodiments, it has been found that in order to improve temperability,the sum of the LTCTE and HTCTE should be greater than 35×10⁻⁷/° C.,37×10⁻⁷/° C., or 40×10⁻⁷/° C. The invention is a novel glass compositionspace that has high coefficients of thermal expansion and Young'smodulus. In some embodiments, it has been found that glass compositionshave improved temperability when the Young's modulus is greater than 67GPa and the temperability factor is greater than or equal to 0.75 (Theapproximate value of commercially available soda-lime glass).

In some embodiments, the glass comprises a combination of SiO₂, Na₂O orK₂O, Al₂O₃, B₂O₃ or ZnO, and alkaline earth oxides. For example,embodiments may comprise from 60 mol % to 72 mol % SiO₂ (60 mol%≤SiO₂≤72 mol %); from greater than 0 mol % Al₂O₃ (0 mol %<Al₂O₃); fromgreater than 0 mol % MgO (0 mol %<MgO); from greater than 0 mol % CaO (0mol %<CaO); 6-16 mol % Na₂O+K₂O (6 mol %≤Na₂O+K₂O≤16 mol %); 0-16 mol %Na₂O (0 mol %≤Na₂O≤16 mol %); 0-16 mol % K₂O (0 mol %≤K₂O≤16 mol %); andone or more of B₂O₃ or ZnO, wherein B₂O₃, when present, comprises 1-10mol % (1 mol %≤B₂O₃≤10 mol %); and ZnO, when present, comprises 3-8 mol% (3 mol %≤ZnO≤8 mol %). Additional aspects of the various constituentsthat can make up the embodied compositions are detailed below.

In some embodiments, the glass comprises a combination of SiO₂, Na₂O orK₂O, Al₂O₃, B₂O₃, and alkaline earth oxides. For example, embodimentsmay comprise from 60 mol % to 65 mol % SiO₂ (60 mol %≤SiO₂≤65 mol %);from 5 mol % to 10 mol % Al₂O₃ (5 mol %≤Al₂O₃≤10 mol %); from 3 mol % to10 mol % MgO (3 mol %≤MgO≤10 mol %); from 5 mol % to 15 mol % CaO (5 mol%≤CaO≤15 mol %); 8-15 mol % Na₂O+K₂O (8 mol %≤Na₂O+K₂O≤15 mol %); 0-15mol % Na₂O (0 mol %≤Na₂O≤15 mol %); 0 mol % to 15 mol % K₂O (0 mol%≤K₂O≤15 mol %); and 1.5 mol % to 6 mol % B₂O₃ (1.5 mol %≤B₂O₃≤6 mol %).

Alternative embodiments may comprise from 65 mol % to 70 mol % SiO₂ (65mol %≤SiO₂≤70 mol %); from >0 mol % to 5 mol % Al₂O₃ (>0 mol %≤Al₂O₃≤5mol %); from 4 mol % to 8 mol % MgO (4 mol %≤MgO≤8 mol %); from 7 mol %to 11 mol % CaO (7 mol %≤CaO≤11 mol %); 9-14 mol % Na₂O+K₂O (9 mol%≤Na₂O+K₂O≤14 mol %); 0-14 mol % Na₂O (0 mol %≤Na₂O≤14 mol %); 0 mol %to 14 mol % K₂O (0 mol %≤K₂O≤14 mol %); and 1 mol % to 6 mol % B₂O₃ (1mol %≤B₂O₃≤6 mol %).

Still other embodiments may comprise from 65 mol % to 70 mol % SiO₂ (65mol %≤SiO₂≤70 mol %); from >0 mol % to 5 mol % Al₂O₃ (>0 mol %≤Al₂O₃≤5mol %); from 5 mol % to 10 mol % MgO (5 mol %≤MgO≤10 mol %); from 6 mol% to 13 mol % CaO (6 mol %≤CaO≤13 mol %); 10-16 mol % Na₂O+K₂O (10 mol%≤Na₂O+K₂O≤16 mol %); 2-16 mol % Na₂O (2 mol %≤Na₂O≤16 mol %); 0 mol %to 8 mol % K₂O (0 mol %≤K₂O≤8 mol %); and 1 mol % to 6 mol % B₂O₃ (1 mol%≤B₂O₃≤6 mol %).

Still other embodiments may comprise from 65 mol % to 72 mol % SiO₂ (65mol %≤SiO₂≤72 mol %); from 4 mol % to 10 mol % Al₂O₃ (4 mol %≤Al₂O₃≤10mol %); from 3 mol % to 10 mol % MgO (3 mol %≤MgO≤10 mol %); from >0 mol% to 13 mol % CaO (0 mol %<CaO≤13 mol %); 10-16 mol % Na₂O+K₂O (10 mol%≤Na₂O+K₂O≤16 mol %); 10-16 mol % Na₂O (10 mol %≤Na₂O≤16 mol %); 0 mol %to 6 mol % K₂O (0 mol %≤K₂O≤6 mol %); and 1.5 mol % to 8 mol % B₂O₃ (1.5mol %≤B₂O₃≤8 mol %).

SiO₂, along with Al₂O₃, B₂O₃, P₂O₅, ZrO₂ and SnO₂, are network formerswhen present in the glass. SiO₂, which is the largest oxide component ofthe glass, may be included to provide high temperature stability andchemical durability. In some embodiments, the glass can comprise from 60to 72 mol % SiO₂. In some embodiments, the glass can comprise from 60 to65 mol % SiO₂. In some embodiments, the glass can comprise from 65 to 72mol % SiO₂. In some embodiments, the glass can comprise from 65-70 mol %SiO₂. In some embodiments, the glass can comprise 60 to 72 mol %, 63 to72 mol %, 65 to 72 mol %, 68 to 72 mol %, 60 to 70 mol %, 63 to 70 mol%, 65 to 70 mol %, 68 to 70 mol %, 60 to 68 mol %, 63 to 68 mol %, 65 to68 mol %, 60 to 65 mol %, 63 to 65 mol %, or 60 to 63 mol % SiO₂. Insome embodiments, the glass comprises 60, 61, 62, 63, 64, 65, 66, 67,68, 69, 70, 71, or 72 mol % SiO₂.

Al₂O₃ may influence the structure of the glass and, additionally, lowerthe liquidus temperature and coefficient of thermal expansion, orenhance the strain point. In some embodiments, the glass can comprisegreater than 0 mol % Al₂O₃. In some embodiments, the glass can comprisefrom >0 to 12 mol % Al₂O₃. In some embodiments, the glass can comprisefrom >0 to 5 mol %, 4 to 10 mol %, 5 to 10 mol % Al₂O₃ or >0 to 3 mol %Al₂O₃. In some embodiments, the glass can comprise from 0.5 to 4 mol %Al₂O₃. In some embodiments, the glass can comprise from >0 to 12 mol%, >0 to 10 mol %, >0 to 8 mol %, >0 to 6 mol %, >0 to 4 mol %, >0 to 2mol %, 1 to 12 mol %, 1 to 10 mol %, 1 to 8 mol %, 1 to 6 mol %, 1 to 4mol %, 1 to 2 mol %, 3 to 8 mol %, 3 to 6 mol %, 3 to 10 mol %, 3 to 12mol %, 5 to 8 mol %, 5 to 10 mol %, 5 to 12 mol %, 7 to 12 mol %, 7 to10 mol %, or 8 to 10 mol % Al₂O₃. In some embodiments, the glass cancomprise about >0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 mol % Al₂O₃.

Without being bound by theory, it is believed that incorporating B₂O₃into the glasses described herein impacts the coefficient of thermalexpansion, especially at high temperatures, and improves thetemperability of the glasses. In some embodiments, the glass cancomprise 1 mol % to 10 mol % B₂O₃. In some embodiments, the glass cancomprise from 1 mol % to 8 mol % or from 1 mol % to 6 mol % B₂O₃. Insome embodiments, the glass can comprise from about 1.5 to 8 mol % B₂O₃or 1.5 to 6 mol % B₂O₃. In some embodiments, the glass can comprise from1 to 4 mol % B₂O₃. In some embodiments, the glass can comprise from 1 to10 mol %, 1.5 to 10 mol %, 2 to 10 mol %, 4 to 10 mol %, 1 to 8 mol %,1.5 to 8 mol %, 2 to 8 mol %, 4 to 8 mol %, 1 to 6 mol %, 1.5 to 6 mol%, 2 to 6 mol %, 4 to 6 mol %, 1 to 4 mol %, 1.5 to 4 mol %, 2 to 4 mol%, 1.5 to 3 mol %, or 1 to 3 mol % B₂O₃. In some embodiments, the glasscan comprise about 0, >0, 1, 2, 3, 4, or 5 mol % B₂O₃.

Zinc oxide, ZnO, may be present and influence the glass properties,including the Young's modulus. In some embodiments, when ZnO is present,the glass can comprise 3 to 8 mol % ZrO₂ or, in some embodiments, from 3to 5 mol % ZnO. In some embodiments, the glass can comprise 3, 4, 5, 6,7, or 8 mol % ZnO.

Without wanting to be bound by theory, it is believed that in someembodiments, the both ZnO and B₂O₃ may have similar effects on thematerial properties. In some embodiments, when B₂O₃ is present in theglass, the glass is free of ZnO. Alternatively, in some embodiments,when ZnO is present in the glass, the glass is free of B₂O₃.

Alkaline earth oxides may improve desirable properties in the materials,including influencing the Young's modulus and the coefficient of thermalexpansion. In some embodiments, the glass comprises from >0 mol % toabout 20 mol % MO (0 mol %≤MO≤20 mol %), where M is the sum of thealkaline earth metals Mg, Ca, Sr, and Ba, in the glass. In someembodiments, the glass can comprise from >0 to 18 mol % MO. In someembodiments, the glass can comprise from >0 to 16 mol % MO. In someembodiments, the glass can comprise about >0, 1, 2, 3, 4, 5, 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 mol % MO.

In some embodiments, the glasses comprise MgO, CaO, or SrO. In someembodiments, the glass can comprise greater than 0 mol % MgO. In someembodiments, the glass can comprise from >0 to 10 mol % MgO. In someembodiments, the glass can comprise from 3 to 10 mol %, 5 to 10 mol %, 5to 8 mol % MgO. In some embodiments, the glass can comprise from >0 to10 mol %, >0 to 8 mol %, >0 to 6 mol %, >0 to 4 mol %, >0 to 2 mol %, 1to 10 mol %, 1 to 8 mol %, 1 to 6 mol %, 1 to 4 mol %, 1 to 2 mol %, 3to 8 mol %, 3 to 6 mol %, 3 to 10 mol %, 5 to 8 mol %, 5 to 10 mol %, 7to 10 mol %, or 8 to 10 mol % MgO. In some embodiments, the glass cancomprise about >0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mol % MgO.

In some embodiments, the glass can comprise greater than 0 mol % CaO. Insome embodiments, the glass can comprise from >0 to 15 mol % CaO. Insome embodiments, the glass can comprise from >0 to 5 mol %, 6 to 13 mol%, 5 to 15 mol %, 7 to 13 mol %, 7 to 11 mol %, 8 to 12 mol % CaO. Insome embodiments, the glass can comprise from >0 to 15 mol %, >0 to 13mol %, >0 to 11 mol %, >0 to 9 mol %, >0 to 7 mol %, >0 to 5 mol %, 1 to15 mol %, 1 to 13 mol %, 1 to 11 mol %, 1 to 9 mol %, 1 to 7 mol %, 1 to5 mol %, 3 to 15 mol %, 3 to 13 mol %, 3 to 11 mol %, 3 to 9 mol %, 3 to7 mol %, 3 to 5 mol %, 5 to 15 mol %, 5 to 13 mol %, 5 to 11 mol %, 5 to9 mol %, 5 to 7 mol %, 7 to 15 mol %, 7 to 13 mol %, 7 to 11 mol %, 7 to9 mol %, 9 to 15 mol %, 9 to 13 mol %, 9 to 11 mol %, 11 to 15 mol %, or11 to 13 mol % CaO. In some embodiments, the glass can compriseabout >0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 mol %CaO.

SrO may be present in some embodiments and in such embodiments, theglass can comprise from 0 to 5 mol % SrO. In some embodiments, the glasscan comprise from >0 to 5 mol % SrO. In some embodiments, the glass cancomprise from about >0 to 3.5 mol % SrO or 0.2 to 3 mol % SrO. In someembodiments, the glass can comprise from 1 to 4 mol % SrO. In someembodiments, the glass can comprise from 0.2 to 5 mol %, 0.2 to 4 mol %,0.2 to 3 mol %, 0.2 to 2 mol %, >0 to 5 mol %, >0 to 4 mol %, >0 to 3mol %, >0 to 2 mol %, 1 to 5 mol %, 1 to 4 mol %, or 1 to 3 mol % SrO.In some embodiments, the glass can comprise about 0, >0, 1, 2, 3, 4, or5 mol % SrO.

Na₂O and K₂O may improve the temperability of the glass and influencethe coefficient of thermal expansion, especially at low temperatures. Insome embodiments, the glass can comprise from 0 to 16 mol % Na₂O. Insome embodiments, the glass can comprise >0 to 15 mol % Na₂O. In someembodiments, the glass can comprise 10 to 16 mol % Na₂O. In someembodiments, the glass can comprise 2 to 16 mol % Na₂O. In someembodiments, the glass can comprise from 0 to 16 mol %, 0 to 15 mol %, 0to 14 mol %, 0 to 10 mol %, 0 to 8 mol %, 0 to 5 mol %, >0 to 16 mol%, >0 to 15 mol %, >0 to 14 mol %, >0 to 10 mol %, >0 to 8 mol %, >0 to5 mol %, 2 to 16 mol %, 2 to 15 mol %, 2 to 14 mol %, 2 to 10 mol %, 2to 8 mol %, 2 to 5 mol %, 5 to 16 mol %, 5 to 15 mol %, 5 to 14 mol %, 5to 10 mol %, 5 to 8 mol %, 8 to 16 mol %, 8 to 15 mol %, 8 to 14 mol %,8 to 10 mol %, 10 to 16 mol %, 10 to 15 mol %, or 10 to 14 mol % Na₂O.In some embodiments, the glass can comprise 0, >0, 1, 2, 3, 4, 5, 6, 7,8, 9, 10, 11, 12, 13, 14, 15, or 16 mol % Na₂O.

In some embodiments, the glass can comprise from 0 to 16 mol % K₂O. Insome embodiments, the glass can comprise >0 to 15 mol % K₂O. In someembodiments, the glass can comprise 0 to 8 mol % K₂O. In someembodiments, the glass can comprise 0 to 6 mol % K₂O. In someembodiments, the glass can comprise from 0 to 16 mol %, 0 to 15 mol %, 0to 14 mol %, 0 to 10 mol %, 0 to 8 mol %, 0 to 5 mol %, >0 to 16 mol%, >0 to 15 mol %, >0 to 14 mol %, >0 to 10 mol %, >0 to 8 mol %, >0 to5 mol %, 2 to 16 mol %, 2 to 15 mol %, 2 to 14 mol %, 2 to 10 mol %, 2to 8 mol %, 2 to 5 mol %, 5 to 16 mol %, 5 to 15 mol %, 5 to 14 mol %, 5to 10 mol %, 5 to 8 mol %, 8 to 16 mol %, 8 to 15 mol %, 8 to 14 mol %,8 to 10 mol %, 10 to 16 mol %, 10 to 15 mol %, or 10 to 14 mol % K₂O. Insome embodiments, the glass can comprise 0, >0, 1, 2, 3, 4, 5, 6, 7, 8,9, 10, 11, 12, 13, 14, 15, or 16 mol % K₂O.

In some embodiments, the total amount of the alkalis Na₂O and K₂O isimportant to the glass properties. In some embodiments, the glass cancomprise 6 to 16 mol % Na₂O+K₂O. In some embodiments, the glass cancomprise 8 to 16 mol % Na₂O+K₂O. In some embodiments, the glass cancomprise 8 to 15 mol % Na₂O+K₂O. In some embodiments, the glass cancomprise 10 to 16 mol % Na₂O+K₂O. In some embodiments, the glass cancomprise 9 to 14 mol % Na₂O+K₂O. In some embodiments, the glass cancomprise from 6 to 16 mol %, 8 to 16 mol %, 10 to 16 mol %, 6 to 15 mol%, 8 to 15 mol %, 10 to 15 mol %, 6 to 14 mol %, 8 to 14 mol %, 10 to 14mol %, 6 to 12 mol %, 8 to 12 mol %, 10 to 12 mol %, 6 to 10 mol %, 8 to10 mol %, or 6 to 8 mol % Na₂O+K₂O. In some embodiments, the glass cancomprise 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16 mol % Na₂O+K₂O.

Na₂O can be useful in the glass for ion exchange and chemical tempering.In some embodiments, the glass comprises from 0 mol % to about 5 mol %Na₂O (0 mol %≤Na₂O≤5 mol %). In some embodiments, the glass can comprisefrom greater than 0 to 5 mol % Na₂O. In some embodiments, the glass cancomprise from about 0 to 3 mol % Na₂O or >0 to 3 mol % Na₂O. In someembodiments, the glass can comprise from 0.5 to 4 mol % Na₂O. In someembodiments, the glass can comprise from 0 to 5 mol %, 0 to 4 mol %, 0to 3 mol %, 0 to 2 mol %, >0 to 5 mol %, >0 to 4 mol %, >0 to 3 mol%, >0 to 2 mol %, 1 to 5 mol %, 1 to 4 mol %, or 1 to 3 mol % Na₂O. Insome embodiments, the glass can comprise about 0, >0, 1, 2, 3, 4, or 5mol % Na₂O.

K₂O may also be useful in ion exchange and may be present in the glassat amounts from 0 mol % to about 10 mol % K₂O (0 mol %≤K₂O≤10 mol %). Insome embodiments, the glass can comprise from >0 to 10 mol % K₂O. Insome embodiments, the glass can comprise from about 0 to 5 mol % K₂Oor >0 to 3 mol % K₂O. In some embodiments, the glass can comprise from0.5 to 4 mol % K₂O. In some embodiments, the glass can comprise from 0to 10 mol %, 0 to 8 mol %, 0 to 5 mol %, 0 to 4 mol %, 0 to 3 mol %, >0to 10 mol %, >0 to 8 mol %, >0 to 5 mol %, >0 to 3 mol %, 1 to 10 mol %,1 to 8 mol %, 1 to 5, 1 to 4 mol %, 1 to 3 mol %, 2 to 10 mol %, 2 to 8mol %, or 2 to 4 K₂O. In some embodiments, the glass can comprise about0, >0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mol % K₂O.

Alkaline earth oxides may provide advantages for ion exchange in theglass, along with improving other properties in the materials. In someembodiments, the glass comprises from 0 mol % to about 10 mol % MO (0mol %≤MO≤10 mol %), where M is the sum of the alkaline earth metals Mg,Ca, Sr, and Ba, in the glass. In some embodiments, the glass cancomprise from 0 to 8 mol % MO. In some embodiments, the glass cancomprise from 0 to 5 mol % MO. In some embodiments, the glass cancomprise from 1 to 8 mol % MO. In some embodiments, the glass cancomprise from 0 to 10 mol %, 0 to 8 mol %, 0 to 6 mol %, 0 to 4 mol %, 1to 10 mol %, 1 to 8 mol %, 1 to 6 mol % 2 to 10 mol %, 2 to 8 mol %, or2 to 6 mol % MO. In some embodiments, the glass can comprise about >0,1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mol % MO.

In some embodiments, the glasses above further comprise a coloringcomponent. The coloring component may comprise, for example, Fe₂O₃,V₂O₅, Cr₂O₃, TiO₂, MnO₂, NiO, ZnO, CuO, NiO, Co₃O₄, rare earth oxides,and combinations thereof. In some cases, the total mol % of coloringcomponent is from 0 to 4 mol %, 0 to 3 mol %, 0 to 2 mol %, 0 to 1 mol%, >0 to 0.1, >0 to 0.5, >0 to 1, >0 to 2, >0 to 3, or >0 to 4 mol %.

Additional components can be incorporated into the glass to provideadditional benefits or may be incorporated as contaminants typicallyfound in commercially-prepared glass. For example, additional componentscan be added as fining agents (e.g., to facilitate removal of gaseousinclusions from melted batch materials used to produce the glass) and/orfor other purposes. In some embodiments, the glass may comprise one ormore compounds useful as ultraviolet radiation absorbers. In someembodiments, the glass can comprise 3 mol % or less MnO, Nb₂O₅, MoO₃,Ta₂O₅, WO₃, SnO₂, Fe₂O₃, As₂O₃, Sb₂O₃, Cl, Br, or combinations thereof.In some embodiments, the glass can comprise from 0 to about 3 mol %, 0to about 2 mol %, 0 to about 1 mol %, 0 to 0.5 mol %, 0 to 0.1 mol %, 0to 0.05 mol %, or 0 to 0.01 mol % MnO, ZnO, Nb₂O₅, MoO₃, Ta₂O₅, WO₃,SnO₂, Fe₂O₃, As₂O₃, Sb₂O₃, Cl, Br, or combinations thereof. In someembodiments, the glass can comprise from 0 to about 3 mol %, 0 to about2 mol %, 0 to about 1 mol %, 0 to about 0.5 mol %, 0 to about 0.1 mol %,0 to about 0.05 mol, or 0 to about 0.01 mol % SnO₂ or Fe₂O₃, orcombinations thereof. The glasses, according to some embodiments, canalso include various contaminants associated with batch materials and/orintroduced into the glass by the melting, fining, and/or formingequipment used to produce the glass.

Non-limiting examples of precursor glasses for forming the embodiedglasses are listed in Table 1, wherein the values of the components arelisted in mol %.

TABLE 1 Sample Glaverbel soda-lime A B C D E F G SiO₂ (mol %) 70.0668.10 67.22 65.43 67.11 69.03 68.48 60.40 B₂O₃ (mol %) 0.00 1.77 3.415.34 4.31 3.13 5.06 1.98 Al₂O₃ (mol %) 1.17 0.95 0.96 0.96 0.99 1.010.97 8.71 MgO (mol %) 6.49 6.77 6.56 6.54 6.69 6.78 4.03 6.63 CaO (mol%) 8.69 9.06 9.01 8.98 9.21 9.44 8.95 9.11 SrO (mol %) 0.00 0.00 0.000.00 0.00 0.00 0.00 0.00 Na₂O (mol %) 13.33 12.86 12.40 12.32 6.39 0.0212.11 12.60 K₂O (mol %) 0.25 0.50 0.43 0.43 5.30 10.60 0.40 0.47 ZnO(mol %) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 SnO₂ (mol %) 0.22 0.020.00 0.00 0.01 0.00 0.01 0.09 LTCTE (10⁻⁷/° C.) 8.8 8.65 8.47 8.42 8.478.16 8.20 8.4 HTCTE (10⁻⁷/° C.) 27.0 33.80 39.20 44.60 43.50 31.90 43.0032.40 Young's Modulus 72.0 76.2 77.2 79.2 76.0 78.8 78.3 78.4 (GPa)Shear Modulus — 31.2 31.9 32.2 31.0 32.3 32.1 32.0 (GPa) Poisson's Ratio— 0.219 0.212 0.229 0.225 0.222 0.219 0.226 Strain Point (° C.) 507 512521 522 532 598 526 557 Anneal Point (° C.) 549 550 557 557 569 643 563598 Softening Point (° C.) 728 714 713 705 733 829 716 774 Density(g/cm³) 2.540 2.519 2.528 2.535 2.509 2.471 2.519 2.539 SOC (TPa⁻¹)2.720 2.730 2.698 2.696 2.728 2.820 2.769 2.868 Refractive Index 1.5201.5236 1.5267 1.5292 1.5247 1.5172 1.5260 1.5272 VFT - a — −1.469 −1.103−1.086 −1.601 −1.736 −1.234 −1.881 VFT - b — 3794.1 3054.6 2868.8 3916.34270.5 3207.9 4625.2 VFT - T₀ — 301.9 367.7 379.2 313.1 376.8 352.2286.4 Liquidus Viscosity — 11088 7677 4886 20712 40459 29243 — (Poise)Temperability, ψ 0.75 0.86 0.92 0.99 1.01 0.96 0.98 0.94 HTCTE + LTCTE35.8 42.45 47.67 53.02 51.97 40.06 51.2 40.8 (10⁻⁷/° C.) SampleGlaverbel soda-lime H I J K L M N SiO₂ (mol %) 70.06 58.76 56.86 57.2357.70 59.66 70.39 70.50 B₂O₃ (mol %) 0.00 3.73 5.52 5.24 5.03 5.53 7.779.76 Al₂O₃ (mol %) 1.17 9.05 9.13 9.19 9.18 9.01 5.99 3.98 MgO (mol %)6.49 6.52 6.50 6.52 6.45 3.94 7.23 7.03 CaO (mol %) 8.69 9.09 9.00 9.169.02 8.75 0.06 0.06 SrO (mol %) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00Na₂O (mol %) 13.33 12.32 12.44 6.52 0.10 12.54 8.47 8.57 K₂O (mol %)0.25 0.46 0.45 6.06 12.44 0.48 0.01 0.01 ZnO (mol %) 0.00 0.00 0.00 0.000.00 0.00 0.00 0.00 SnO₂ (mol %) 0.22 0.09 0.09 0.09 0.09 0.09 0.05 0.05LTCTE (10⁻⁷/° C.) 8.8 8.32 8.36 8.93 8.89 8.25 5.89 5.79 HTCTE (10⁻⁷/°C.) 27.0 34.00 27.90 36.00 27.00 42.00 28.07 32.70 Young's Modulus 72.078.3 78.3 75.8 68.0 77.6 69.71 70.74 (GPa) Shear Modulus — 31.9 31.830.6 27.6 31.6 28.89 29.44 (GPa) Poisson's Ratio — 0.226 0.232 0.2380.229 0.229 0.206 0.202 Strain Point (° C.) 507 543 536 541 589 537 543532 Anneal Point (° C.) 549 584 576 583 634 577 587 575 Softening Point(° C.) 728 757 740 758 — 742 812 766 Density (g/cm³) 2.540 2.536 2.5352.52 2.486 2.521 2.363 2.363 SOC (TPa⁻¹) 2.720 2.783 2.792 2.843 2.8612.737 3.398 3.345 Refractive Index 1.520 1.5289 1.5298 1.5266 1.52121.5264 1.4951 1.4964 VFT - a — −1.514 −1.345 −1.994 −2.387 −1.441 −3.154−2.402 VFT - b — 3916.1 3518.8 4730.7 5460.2 3873 9067.9 7058.4 VFT - T₀— 335.4 354.3 271.2 296 319.3 −54.2 44.4 Temperability, ψ 0.75 0.94 0.940.81 0.99 0.82 0.75 0.76 HTCTE + LTCTE 35.8 42.32 36.26 44.93 35.8950.25 33.96 38.49 (10⁻⁷/° C.) Sample Glaverbel soda-lime O P Q R S T USiO₂ (mol %) 70.06 70.53 70.70 70.71 70.55 63.11 62.26 63.12 B₂O₃ (mol%) 0.00 7.80 9.67 7.62 7.77 0 0 0 Al₂O₃ (mol %) 1.17 6.02 4.01 3.99 4.0011.58 11.41 10.58 MgO (mol %) 6.49 4.97 5.06 7.01 8.98 0.00 0.00 0.00CaO (mol %) 8.69 0.04 0.04 0.06 0.07 0.00 0.00 0.00 SrO (mol %) 0.000.00 0.00 0.00 0.00 0.00 0.00 0.00 Na₂O (mol %) 13.33 10.54 10.42 10.518.54 16.43 16.81 16.41 K₂O (mol %) 0.25 0.01 0.01 0.01 0.01 1.88 1.941.89 ZnO (mol %) 0.00 0.00 0.00 0.00 0.00 1.93 3.12 1.94 SnO₂ (mol %)0.22 0.05 0.05 0.05 0.05 0.05 0.05 0.05 LTCTE ((10⁻⁷/° C.) 8.8 6.47 6.396.57 5.88 10.3 10.31 10.19 HTCTE (10⁻⁷/° C.) 27.0 34.44 34.01 35.9932.70 17.62 18.82 17.30 Young's Modulus 72.0 70.05 71.50 72.19 71.9166.19 67.78 65.22 (GPa) Shear Modulus — 29.23 29.79 29.99 29.85 27.4427.99 27.03 (GPa) Poisson's Ratio — 0.198 0.201 0.203 0.203 0.206 0.210.207 Strain Point (° C.) 507 532 522 531 545 615 605 628 Anneal Point(° C.) 549 576 564 573 584 672 661 688 Softening Point (° C.) 728 778748 758 780 912 927 911 Density (g/cm³) 2.540 2.379 2.383 2.393 2.3792.432 2.459 2.414 SOC (TPa⁻¹) 2.720 3.287 3.284 3.225 3.289 3.104 3.1083.107 Refractive Index 1.520 1.497 1.4982 1.4991 1.4982 1.4902 1.49481.4862 VFT - a — −2.120 −1.385 −2.166 −2.528 −2.656 −2.515 −1.732 VFT -b — 6504.5 4601.5 6190.8 7167.1 7560.6 7279.9 5405.9 VFT - T₀ — 89.2231.8 112.9 62.2 90.7 109.2 273.5 Temperability, ψ 0.75 0.84 0.79 0.840.78 0.77 0.83 0.75 HTCTE + LTCTE 35.8 40.91 40.4 42.56 38.58 27.9229.13 27.49 (10⁻⁷/° C.) Sample Glaverbel soda-lime V W X Y Z SiO₂ (mol%) 70.06 63.29 60.87 65.43 62.23 62.53 B₂O₃ (mol %) 0.00 0.00 0.00 16.865.90 5.98 Al₂O₃ (mol %) 1.17 9.58 11.52 3.7 0.96 0.96 MgO (mol %) 6.490.00 0.00 0.00 6.49 6.37 CaO (mol %) 8.69 0.00 0.00 0.00 9.07 8.96 SrO(mol %) 0.00 0.00 0.00 3.06 0.00 0.00 Na₂O (mol %) 13.33 16.34 16.636.47 12.79 12.64 K₂O (mol %) 0.25 1.90 1.87 0 0.47 0.46 ZnO (mol %) 0.002.93 2.94 0 0.00 0.00 SnO₂ (mol %) 0.22 0.05 0.05 0.05 0.11 0.11 Fe₂O₃(mol %) 0.03 0.05 TiO₂ (mol %) 1.96 1.93 LTCTE (10⁻⁷/° C.) 8.8 10.4510.08 6.22 HTCTE (10⁻⁷/° C.) 27.0 17.02 18.00 39.36 Young's Modulus 72.065.64 65.84 78.53 (GPa) Shear Modulus — 27.37 27.17 32.41 (GPa)Poisson's Ratio — 0.199 0.213 0.212 Strain Point (° C.) 507 638 612 492Anneal Point (° C.) 549 700 671 527 Softening Point (° C.) 728 931 907673 Density (g/cm³) 2.540 2.425 2.442 2.432 SOC (TPa⁻¹) 2.720 3.1493.149 3.105 Refractive Index 1.520 1.4867 1.4903 1.5116 VFT - a — −0.116−2.665 −0.779 VFT - b — 2364 7338.2 2734.7 VFT - T₀ — 629.2 118.9 347.9Temperability, ψ 0.75 0.78 0.76 0.79 HTCTE + LTCTE 35.8 27.47 28.0845.58 (10⁻⁷/° C.)

In addition to having high fracture toughness, the glasses describedherein can have color and transparency/translucency properties that makethem advantageous for a number of applications. The glasses of one ormore embodiments may exhibit a substantially white, white-clear, gold oramber color, or other colors as well. In some embodiments, the glassesexhibit a color presented in SCE color space coordinates (determinedfrom reflectance spectra measurements using a spectrophotometer, withilluminant D65 and specular reflectance excluded), of the followingranges: a*=from about −5 to about −1; b*=from about 5 to about 18; andL*>83. In some applications, the glasses are transparent andquantitatively white to yellow-brown in color and are of particularinterest in photovoltaic applications.

Color examples are shown in Table 2. The first four columns of the tablehave the color coordination of thin-line PV cell, and the colorcoordination when the glass is on the top of the PV cell (thickness ofthe glass is 2 mm or 4 mm). The last four columns are the colorcoordination for the glass itself.

SCE color L* a* b* SCE color L* a* b* PV cell thin lines 19.09 8.43 —Comp. Y (2 mm 15.03 6.14 −8.62 Comp. Y (2 mm) 86.76 — 9.14 Comp. Y (4 mm13.69 4.48 −5.54 Comp. Y (4 mm) 82.63 — 15.11 Comp. Z (2 mm 14.96 7 —Comp. Z (2 mm) 88.07 — 6.72 Comp. Z (4 mm 13.73 5.56 −7.65 Comp. Z (4mm) 84.43 — 12.21 SCI color L* a* b* SCI color L* a* b* PV cell thinlines 19.25 7.99 — Comp. Y (2 mm 38.56 1.66 −2.85 Comp. Y (2 mm) 91.89−2.4 8.72 Comp. Y (4 mm 37.43 0.66 −0.52 Comp. Y (4 mm) 87.81 −4.3 14.47Comp. Z (2 mm 38.04 1.23 −1.72 Comp. Z (2 mm) 93.2 — 6.31 Comp. Z (4 mm38.76 2.11 −4   Comp. Z (4 mm) 89.63 — 11.59Wherein L* indicates lightness, a* is the red/green coordinate, and b*is the yellow/blue coordinate. Deltas for L* (ΔL*), a* (Δa*) and b*(Δb*) may be positive (+) or negative (−). From specular componentexcluded (SCE) color coordination, all the glasses make the PV celldarker, and move the color to less red and less blue. Less blue color ismore aesthetically desirable for the appearance when combined with thePV cell.

As shown in FIG. 1 , the transmittance of visible light (390-700 nm) isabove 60% for all glasses and generally over 80% at the center (˜550nm). Generally, solar cells are made out of N-type and P-typesemiconductor materials that use the visual light wavelengths of 380 nmto 750 nm to generate electricity. Therefore, these glasses with theembodied color components (e.g, the darkest color, being Comp. Z, 4 mm)won't reduce the efficiency of solar cell significantly.

In some embodiments, the glass can be strengthened to includecompressive stress (CS) that extends from a surface thereof to a depthof compression (DOC). The compressive stress regions are balanced by acentral portion exhibiting a tensile stress. At the DOC, the stresscrosses from a positive (compressive) stress to a negative (tensile)stress.

As an alternative to thermal tempering, the glasses disclosed herein maybe ion exchanged by immersion in at least one ion exchange bathcontaining molten salts (e.g., nitrates, sulfides, halides, or the like)of at least one alkali metal such as lithium, sodium, or potassium. Ionexchange is commonly used to chemically strengthen glasses. In oneparticular example, alkali cations within a source of such cations(e.g., a molten salt, or “ion exchange,” bath) are exchanged withsmaller alkali cations within the glass to achieve a layer under acompressive stress (CS) extending from the surface of the glass to adepth of compression (DOC) within the glass phase. For example,potassium ions from the cation source are often exchanged with sodiumand/or lithium ions within the glass phase, and the K⁺ concentrationprofile correlates with the compressive stress and depth of layer. Theion exchange bath may contain a salt (or salts) of a single alkali metal(e.g., sulfides, nitrates, or halides of Li, Na, or K) or salts of twoor more alkali metals (e.g., sulfides, nitrates, or halides of Li andNa, or sulfides, nitrates, or halides of Na and K). Ion exchange iscarried out in the ion exchange bath at temperatures ranging from about390° C. to about 550° C. for times ranging from about 0.5 hour to about24 hours.

The glass, in some embodiments, is ion exchanged and has a compressivelayer extending from a surface to a depth of compression (DOC) of atleast about 10 μm or, in some embodiments, at least about 30 μm into theglass, or in some embodiments up to about 10, 15, 20 or 25% into theglass as measured by thickness (surface to center). In some embodiments,the compressive layer extends from the surface of the glass to a depthof up to about 20% of the thickness of the glass. In some embodiments,the glass may be strengthened to exhibit a surface compressive stress ina range from 250 MPa to 800 MPa or greater.

In the strengthened glass, the depth of the compressive layer may bedetermined by electron microprobe, glow-discharge optical emissionspectroscopy (GDOES, which is a technique for measuring depth profilesof constituent elements in a solid sample by detecting emissions fromatoms accommodated in plasma by sputtering), or similar techniques thatcan provide composition data as a function of depth, where data wouldshow incorporation of Na (where Na⁺ replaces Li⁺ in the glass phase)and/or K at the surfaces. The DOC of a precursor glass may be measuredby surface stress meter (FSM) using commercially available instrumentssuch as the FSM-6000, manufactured by Orihara Industrial Co., Ltd.(Japan). Surface stress measurements rely upon the accurate measurementof the stress optical coefficient (SOC), which is related to thebirefringence of the glass. SOC in turn is measured by those methodsthat are known in the art, such as fiber and four point bend methods,both of which are described in ASTM standard C770-98 (2013), entitled“Standard Test Method for Measurement of Glass Stress-OpticalCoefficient,” the contents of which are incorporated herein by referencein their entirety, and a bulk cylinder method. CS may also be measuredby measured by FSM. As used herein CS may be the “maximum compressivestress” which is the highest compressive stress value measured withinthe compressive stress layer. In some embodiments, the maximumcompressive stress is located at the surface of the glass. In otherembodiments, the maximum compressive stress may occur at a depth belowthe surface, giving the compressive profile the appearance of a “buriedpeak.”

The thermally or chemically strengthened glasses or articles disclosedherein may be incorporated into another article such as an article witha display (or display articles) (e.g., consumer electronics, includingmobile phones, tablets, computers, navigation systems, and the like),architectural articles (e.g., windows, skylights, shingles),transportation articles (e.g., automotive, trains, aircraft, sea craft,etc.), appliance articles, or any article that would benefit fromtransparency, scratch-resistance, abrasion resistance or a combinationthereof. In other embodiments, the glass forms a portion of a consumerelectronic product, such as a cellular phone or smart phone, laptopcomputer, tablet, or the like. Such consumer electronic productstypically comprise a housing having front, back, and side surfaces, andinclude electrical components such as a power source, a controller, amemory, a display, and the like, which are at least partially internalto the housing. In some embodiments, the glass described hereincomprises at least a portion of a protective element, such as, but notlimited to, the housing and/or display of a consumer electronic product.

Processes for Making Glasses

Glasses having the oxide contents listed in Table 1 can be made viatraditional methods. For example, in some embodiments, the precursorglasses can be formed by thoroughly mixing the requisite batch materials(for example, using a turbular mixer) in order to secure a homogeneousmelt, and subsequently placing into silica and/or platinum crucibles.The crucibles can be placed into a furnace and the glass batch meltedand maintained at temperatures ranging from 1250-1650° C. for timesranging from about 6-16 hours. The melts can thereafter be poured intosteel molds to yield glass slabs. Subsequently, those slabs can betransferred immediately to an annealer operating at about 500-650° C.,where the glass is held at temperature for about 1 hour and subsequentlycooled overnight. In another non-limiting example, precursor glasses areprepared by dry blending the appropriate oxides and mineral sources fora time sufficient to thoroughly mix the ingredients. The glasses aremelted in platinum crucibles at temperatures ranging from about 1100° C.to about 1650° C. and held at temperature for about 16 hours. Theresulting glass melts are then poured onto a steel table to cool. Theprecursor glasses are then annealed at appropriate temperatures.

Tempering of the embodied glasses was achieved using conventionalprocesses wherein the glasses were heated in a radiant energy furnace ora convection furnace (or a “combined mode” furnace using bothtechniques) to a predetermined temperature, then gas cooling(“quenching”), typically via convection by blowing large amounts ofambient air against or along the glass surface.

Examples

Embodied glasses can be made as described herein. The properties ofGlaverbel soda lime glass (SLG) are compared to the properties of theembodied glasses. Properties of the glasses are shown in Table 1. Inaddition, the surface compression composition C is compared to GlaverbelSLG for 1 mm thick glass slabs in Table 3. Composition C shows atemperability value of 0.99, approximately 32% higher than SLG and iscapable of obtaining a surface compression of 145 MPa vs 105 MPa for SLGunder equivalent tempering conditions.

TABLE 2 Surface H T₀ Thickness Compression Glass ψ (cal/(cm²-s-K)) (°C.) (mm) (MPa) Glaverbel 0.75 0.039 690 1.05 105 Comp. C 0.99 0.039 6801.03 145

While typical embodiments have been set forth for the purpose ofillustration, the foregoing description should not be deemed to be alimitation on the scope of the disclosure or appended claims.Accordingly, various modifications, adaptations, and alternatives mayoccur to one skilled in the art without departing from the spirit andscope of the present disclosure or appended claims.

1. A glass composition comprising: 60-72 mol % SiO₂ greater than 0 mol %Al₂O₃ greater than 0 mol % MgO greater than 0 mol % CaO 6-16 mol %Na₂O+K₂O 0-16 mol % Na₂O 0-16 mol % K₂O and one or more of B₂O₃ or ZnO,wherein: B₂O₃, when present, comprises 1-10 mol %; and ZnO, whenpresent, comprises 3-8 mol %.
 2. The glass composition of claim 1,comprising >0-10 mol % MgO.
 3. The glass composition of claim 1,comprising >0-12 mol % Al₂O₃.
 4. The glass composition of claim 1,comprising >0-15 mol % CaO.
 5. The glass composition of claim 1,comprising 8-16 mol % Na₂O+K₂O.
 6. The glass composition of claim 1,comprising >0-15 mol % Na₂O.
 7. The glass composition of claim 1,comprising 1.5-8 mol % B₂O₃ and is free of ZnO.
 8. The glass compositionof claim 1, wherein the glass composition has a low temperaturecoefficient of thermal expansion (LTCTE) measured at 25° C. and a hightemperature coefficient of thermal expansion (HTCTE) measured at 300°C., and wherein the sum of the LTCTE and the HTCTE is 35×10⁻⁷/° C. orgreater.
 9. The glass composition of claim 1, wherein the sum of theLTCTE and the HTCTE is 37×10⁻⁷/° C. or greater.
 10. The glasscomposition of claim 9, wherein the sum of the LTCTE and the HTCTE is40×10⁻⁷/° C. or greater.
 11. The glass composition of claim 1, whereinthe glass composition has a temperability, ψ, and the temperability, ψ,is equal to or greater than 0.80.
 12. The glass composition claim 1,wherein the temperability, ψ, is equal to or greater than 0.85.
 13. Theglass composition claim 12, wherein the temperability, ψ, is equal to orgreater than 0.90.
 14. A glass composition, comprising: 60-65 mol % SiO₂5-10 mol % Al₂O₃ 3-10 mol % MgO 5-15 mol % CaO 8-15 mol % Na₂O+K₂O 0-15mol % Na₂O 0-15 mol % K₂O 1.5-6 mol % B₂O₃; and wherein the glasscomposition has a low temperature coefficient of thermal expansion(LTCTE) measured at 25° C. and a high temperature coefficient of thermalexpansion (HTCTE) measured at 300° C., and wherein the sum of the LTCTEand the HTCTE is 35×10⁻⁷/° C. or greater; and the glass composition hasa temperability, ψ, and the temperability, ψ, is equal to or greaterthan 0.80.
 15. The glass composition of claim 14, wherein sum of theLTCTE and the HTCTE is 40×10⁻⁷/° C. or greater.
 16. The glasscomposition of claim 14, wherein the temperability, ψ, is equal to orgreater than 0.90.
 17. A glass composition, comprising: 65-70 mol %SiO₂ >0-5 mol % Al₂O₃ 5-10 mol % MgO 6-13 mol % CaO 10-16 mol % Na₂O+K₂O2-16 mol % Na₂O 0-8 mol % K₂O 1-6 mol % B₂O₃; and wherein the glasscomposition has a low temperature coefficient of thermal expansion(LTCTE) measured at 25° C. and a high temperature coefficient of thermalexpansion (HTCTE) measured at 300° C., and wherein the sum of the LTCTEand the HTCTE is 40×10⁻⁷/° C. or greater; and the glass composition hasa temperability, ψ, and the temperability, ψ, is equal to or greaterthan 0.80.
 18. The glass composition of claim 17, wherein thetemperability, ψ, is equal to or greater than 0.90.
 19. The glasscomposition of claim 1, comprising: 65-70 mol % SiO₂ >0-5 mol % Al₂O₃4-8 mol % MgO 7-11 mol % CaO 9-14 mol % Na₂O+K₂O 0-14 mol % Na₂O 0-14mol % K₂O 1-6 mol % B₂O₃; and wherein the glass composition has a lowtemperature coefficient of thermal expansion (LTCTE) measured at 25° C.and a high temperature coefficient of thermal expansion (HTCTE) measuredat 300° C., and wherein the sum of the LTCTE and the HTCTE is 35×10⁻⁷/°C. or greater; and the glass composition has a temperability, ψ, and thetemperability, ψ, is equal to or greater than 0.80.
 20. The glasscomposition of claim 19, wherein the temperability, ψ, is equal to orgreater than 0.90.
 21. The glass composition of claim 19, wherein thesum of the LTCTE and the HTCTE is 37×10⁻⁷/° C. or greater.
 22. The glasscomposition claim 19, wherein the sum of the LTCTE and the HTCTE is40×10⁻⁷/° C. or greater.
 23. The glass composition of claim 19, whereinthe glass composition when rolled into a 2 mm thick slab has atransmission and wherein the transmission is greater than 80% at 575 nm.